EP4251694A1 - Polyolefin compositions obtained from recycled polyolefins - Google Patents

Polyolefin compositions obtained from recycled polyolefins

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Publication number
EP4251694A1
EP4251694A1 EP21805988.9A EP21805988A EP4251694A1 EP 4251694 A1 EP4251694 A1 EP 4251694A1 EP 21805988 A EP21805988 A EP 21805988A EP 4251694 A1 EP4251694 A1 EP 4251694A1
Authority
EP
European Patent Office
Prior art keywords
component
anyone
iso
weight
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21805988.9A
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German (de)
French (fr)
Inventor
Claudio Cavalieri
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Poliolefine Italia SRL
Original Assignee
Basell Poliolefine Italia SRL
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basell Poliolefine Italia SRL filed Critical Basell Poliolefine Italia SRL
Publication of EP4251694A1 publication Critical patent/EP4251694A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic

Definitions

  • the present disclosure relates to compositions containing recycled polypropylene that can be advantageously used for the production of blow molding articles.
  • Polyolefins in particular polypropylene, are increasingly consumed in large amounts for many applications, including packaging for food and other goods, fibers, automotive components, and a great variety of manufactured articles.
  • polypropylene are increasingly consumed in large amounts for many applications, including packaging for food and other goods, fibers, automotive components, and a great variety of manufactured articles.
  • the said massive use of polyolefins is creating a concern as regards the environmental impact of the waste materials generated after the first use.
  • compatibilizer ingredients have been proposed in the art.
  • US5,030,662 discloses the use of compatibilizer of the type that reacts with the polymer matrix under heat and shearing conditions either by free radical or ionic mechanism.
  • compatibilizers according to this document are olefin copolymers with polar monomers such as maleic anhydride or vinyl acetate.
  • W02007/071494 discloses the use of a a heterophasic polyolefin composition having flexural modulus equal to or lower than 600 MPa as a compatibilizer agent for a recycled polyolefin composition.
  • the effect of the compatibilizer was that of improving the mechanical properties while the optical properties had not been tested.
  • improving the optical properties of polyolefin composition including substantial amounts of recycled material is a demanding task because the multiplicity of components chemically different to each other makes certain optical properties such as transparency difficult to be achieved at a satisfactory extent.
  • the use of recycled material in applications requiring a certain level of transparency, i.e., translucent applications is strongly discouraged.
  • polypropylene composition comprising, or consisting essentially of, (per cent by weight):
  • (b3)- from 1 to 5% preferably from 2 to 4%, by weight of an ethylene homo or copolymer containing up to 30% wt of a C3-C10 alpha olefin.
  • copolymer refers to both polymers with two different recurring units and polymers with more than two different recurring units, such as terpolymers, in the chain.
  • ambient temperature is meant therein a temperature of about 25 °C (room temperature).
  • the term “consisting essentially of’, as used herein in connection with a polymer or polymer composition means that, in addition to those components which are mandatory, other components may also be present in the polymer or in the polymer composition, provided that the essential characteristics of the polymer or of the composition are not materially affected by their presence.
  • examples of components that, when present in customary amounts in a polymer or in a polymer composition, do not materially affect their characteristics are the catalyst residues, antistatic agents, melt stabilizers, light stabilizers, antioxidants, antiacids.
  • crystalline polypropylene is meant in the present application a propylene polymer having an amount of isotactic pentads (mmmm), measured by 13 C-MNR on the fraction insoluble in xylene at 25° C, higher than 70 molar %; by “elastomeric” polymer is meant a polymer having solubility in xylene at ambient temperature higher than 50 wt%.
  • any component (a) to (b3) and any preferred range of features of components (a) to (b3) can be combined with any preferred range of one or more of the features of components (a) to (b3) and with any possible additional component, and its features, described in the present disclosure.
  • the component (a), which is preferably a virgin resin, can be a propylene homopolymer, a random copolymer of propylene containing up to 7%, preferably 0.2 to 6% of ethylene, or a random terpolymer of propylene containing in addition to ethylene up to 4% by weight, also up to 6% by weight, preferably from 1 to 5%, of a C4-C10 a-olefin.
  • Illustrative C4-C10 a-olefin include 1 -butene, 1-pentene, 1 -hexene, 4-methyl-l-pentene and 1-octene, with 1 -butene being particularly preferred.
  • Component (a) has a content of polymer fraction which is insoluble in xylene at room of not less than 80%, more preferably not less than 85%, and most preferably not less than 90% by weight.
  • the content of polymer which is insoluble in xylene at room temperature is not less than 90%, more preferably not less than 95% and most preferably not less than 97% by weight.
  • the melt flow rate (ISO 1133 230°C/2.16 kg) of component (a) preferably ranges from 0.5 to 3g/10’ and preferably from 1 to 3 g/10’.
  • the melting temperature of the component (a) preferably ranges from 135 to 165°C.
  • component (a) is a homopolymer
  • the melting temperature determined via DSC, preferably ranges from 155 to 165°C while for a copolymer it preferably ranges from 135 to 155°C.
  • Component (a) can be prepared by polymerizing propylene, optionally in mixture with ethylene and C4-C10 a-olefin in the presence of a catalyst comprising the product of the reaction between:
  • a solid catalyst component comprising Ti, Mg, Cl, and at least an internal electron donor compound
  • R 7 , R 8 , and R 9 are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms.
  • the internal donor is preferably selected from the esters of mono or dicarboxylic organic acids such as benzoates, malonates, phthalates and certain succinates. Examples of internal donors are described in US 4522930A, EP 045977A2 and international patent applications WO 00/63261 and WO 01/57099. Particularly suited are the phthalic acid esters and succinate acids esters. Alkylphthalates are preferred, such as diisobutyl, dioctyl and diphenyl phthalate and benzyl- butyl phthalate.
  • the particles of solid component (i) may have substantially spherical morphology and average diameter ranging between 5 and 150 pm, preferably from 20 to 100 pm and more preferably from 30 to 90 pm.
  • particles having substantially spherical morphology those are meant wherein the ratio between the greater axis and the smaller axis is equal to or lower than 1.5 and preferably lower than 1.3.
  • the amount of Mg may preferably range from 8 to 30% more preferably from 10 to
  • the amount of Ti may range from 0.5 to 7% and more preferably from 0.7 to 5wt.
  • the solid catalyst component (i) can be prepared by reacting a titanium compound of formula Ti(OR)q-yXy, where q is the valence of titanium and y is a number between 1 and q, preferably TiCU, with a magnesium chloride deriving from an adduct of formula MgC12*pROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms.
  • the adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride, operating under stirring conditions at the melting temperature of the adduct (100-130°C).
  • the adduct is mixed with an inert hydrocarbon immiscible with the adduct thereby creating an emulsion which is quickly quenched causing the solidification of the adduct in form of spherical particles.
  • spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648.
  • the so obtained adduct can be directly reacted with Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130°C) so as to obtain an adduct in which the number of moles of alcohol is of lower than 3, preferably between 0.1 and 2.5.
  • the reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCU; the mixture is heated up to 80-130°C and kept at this temperature for 0.5-2 hours.
  • the treatment with TiC14 can be carried out one or more times.
  • the electron donor compound can be added in the desired ratios during the treatment with TiCU.
  • the alkyl-Al compound (ii) is preferably chosen among the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri- n-hexylaluminum, tri-n-octylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides, such as AlEt2Cl and AhE CU, possibly in mixture with the above cited trialkylaluminums.
  • the Al/Ti ratio is higher than 1 and may preferably range between 50 and 2000.
  • silicon compounds (iii) in which a is 1, b is 1, c is 2, at least one of R 7 and R 8 is selected from branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms optionally containing heteroatoms and R9 is a Cl -CIO alkyl group, in particular methyl.
  • Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), diisopropyldimethoxysilane, (2-ethylpiperidinyl)t-butyldimethoxysilane, (2- ethylpiperidinyl)thexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2- ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane.
  • C donor methylcyclohexyldimethoxysilane
  • D donor dicyclopentyldimethoxysilane
  • diisopropyldimethoxysilane (2-ethy
  • the external electron donor compound (iii) is used in such an amount to give a molar ratio between the organoaluminum compound and said external electron donor compound (iii) of from 0.1 to 200, preferably from 1 to 100 and more preferably from 3 to 50.
  • the polymerization process can be carried out in gas-phase, operating in one or more fluidized or mechanically agitated bed reactors, slurry polymerization using as diluent an inert hydrocarbon solvent, or bulk polymerization using the liquid monomer (for example propylene) as a reaction medium.
  • liquid monomer for example propylene
  • Component (b) can origin either from post-consumer waste (PostCW) or from pre consumer waste (Pre-CW). Preferably, it origins from Pre-CW.
  • PostCW post-consumer waste
  • Pre-CW pre consumer waste
  • the pre-consumer plastic is regarded as a plastic waste diverted from a manufacturing process which is not reutilized such as rework, regrind or scrap, and is not reincorporated in the same process that generated it.
  • Component (bl) is preferably a random copolymer of propylene containing from 1 to 6%, preferably 2 to 5% of ethylene. It may derive from pre-consumer random PP material used for example packaging.
  • Component (b2) is preferably selected from the group consisting of SBS and SEBS rubbers which are (partly) hydrogenated styrene-(ethylene-butadiene)-styrene block copolymers. These polymers are triblock copolymers, having styrene at both extremities of the polymer chain with an internal polybutadiene or ethylene/butadiene, polyisoprene or hydrogenated polybutadiene or polyisoprene block.
  • SBC copolymers are obtained via anionic polymerization and are commercially available, for example under the tradenames of Kraton and Tuftec, such as for example Kraton SEBS G1657MS.
  • component (b2) is preferably derived from pre-consumer source.
  • component (b3) is present in an amount ranging from 1 to 5% preferably from 2 to 4%, by weight. It is preferably an ethylene polymer containing up to 30%, preferably up to 20%, more preferably up to 15% by weight of a C3-C10 alpha olefin.
  • the alpha olefin is selected from butene- 1, hexene- 1 and octene-1.
  • the ethylene polymer is preferably selected from LDPE, LLDPE, VLDPE and polyolefin elastomers (POE) of pre-consumer source.
  • the melt flow rate (ISO 1133 230°C/2.16 kg) of the whole component (b) can generally range from 0.5 to 30 g/10’, preferably from 1 to 25 glO’ and more preferably from 2 to
  • the component (b) according to the present disclosure preferably has a tensile modulus lower than 500 MPa, preferably lower than 400 MPa.
  • the composition forming the component (b) of the present disclosure has preferably a Charpy impact strength at 23°C of 50-100 kJ/m 2 , more preferably between 55-80 kJ/m 2 .
  • the Charpy impact strength at -30°C preferably ranges from 5 to 20 kJ/m 2 , more preferably between from 6 to 15 kJ/m 2 .
  • the component (b) of the present disclosure may exhibit an elongation at break equal to or higher than 400%, and more preferably in the range 500- 600%.
  • the melting temperature of component (b) ranges from 140 to 160°C preferably from 145 to 155°C.
  • the final melt flow rate (ISO 1133 230°C/2.16 kg) of the whole polypropylene composition ranges from 0.1 to 5g/10’ preferably from 0.5 to 3 g/10’.
  • the polypropylene composition can further comprise between 0.05-10wt%, preferably 0.1-8 wt%, of additives.
  • Additives may comprise, stabilizers, peroxides, calcium oxides (CaO) or colorants, nucleants, clarifiers and stripping agents.
  • a stabilizer can be added, such as for example masterbatches like Tosaf ME
  • 833848 which is a blend of about 70 wt% LDPE with a phenolic stabilizer (Irganox B225) and an Irgafos.
  • a masterbatch is added in an amount between 0.2 and 1.5 wt%, preferably between 0.3 and 1.2 wt%.
  • a peroxide in the form of an organic compound or masterbatch can be added.
  • the peroxide improves the flow of the material and can be used to achieve a desired melt flow.
  • the peroxide can for example be selected from the group of Zebraflow T028,
  • Zebraflow T0214 or Zebraflow T0318 which are masterbatches of a peroxide with a polyolefin.
  • the specific amount of peroxide is determined by the skilled in the art having in mind the melt flow rate of the single components, their respective amounts and the final desired melt flow rate.
  • the peroxide can amount to 2-10 wt% of the entire additive package.
  • a CaO can be added to inhibit release of HC1.
  • the CaO can be also added as a masterbatch with for example LDPE.
  • CaO can for example be added in a range between 0-2 wt%.
  • a black colorant can for example be added to the polymer composition between
  • Stripping agents are compounds used to remove volatiles during processing of the composition.
  • BYK 4200 is one of the commercially available products.
  • the amount of the whole package of additives ranges from 0.5 to 7%wt preferably from 1 to 6%wt based on the total amount of the polypropylene composition.
  • the polypropylene composition consists of the following components (per cent by weight):
  • (b2) from 5 to 30, preferably from 7 to 25% by weight of a styrenic block copolymer (SBC) and, (b3) from 1 to 5% preferably from 2 to 4%, by weight of an ethylene homo or copolymer containing up to 30% wt of a C3-C10 alpha olefin; said polypropylene composition further consisting of - 0.05- 10 wt%, preferably 0.1-8 wt%, of additives.
  • SBC styrenic block copolymer
  • the propylene polymer composition according to the present disclosure preferably has a tensile modulus ranging between 800-1400 MPa, preferably between 870-1200 MPa.
  • the polymer composition preferably has a Charpy impact strength at 23 °C of 50-
  • the Charpy impact strength at 0°C ranges from 5 to 20 kJ/m 2 , more preferably between from 6 to 15 kJ/m 2 .
  • composition of the present disclosure may exhibit a stress at yield equal to or higher than 15 MPa, an elongation at break equal to or higher than 500%, and more preferably higher than 550% and even more preferably equal to or higher than 580%.
  • composition of the present disclosure shows a haze level below 30%, preferably below 25% and more preferably below 20%.
  • composition of the present disclosure can be obtained by mechanical blending of the components (a)-(b) and optionally further components and additives according to conventional techniques.
  • process of making the polymer composition may use a co-rotating twin screw tandem extruder to which the components (a-b) and optionally further components and additives are added.
  • Additives can be added in a reclaim extruder (first extruder) and a compounding extruder (second extruder) of a tandem extruder.
  • the polypropylene polymer composition can be presented in granule or flake form to be used for manufacturing articles.
  • the polypropylene polymer composition of the present disclosure can be used in a variety of applications where an optical/mechanical balance is required. Accordingly, they are suitable for use in the manufacturing of extruded and/or thermoformed articles and particularly suitable for manufacturing blow molded articles and in particular bottles.
  • the content of the xylene-soluble fraction is expressed as a percentage of the original 2.5 grams and then, by the difference (complementary to 100%), the xylene insoluble percentage (%);
  • the sample is dissolved in tetrahydronaphthalene at 135 °C and then poured into a capillary viscometer.
  • the viscometer tube (Ubbelohde type) is surrounded by a cylindrical glass jacket; this setup allows for temperature control with a circulating thermostatic liquid.
  • the downward passage of the meniscus is timed by a photoelectric device.
  • the tacticity of Propylene sequences was calculated as mm content from the ratio of the PPP mmTpp (28.90-29.65 ppm) and the whole Tpp (29.80-28.37 ppm).
  • Elongation at yield measured according to ISO 527.
  • Elongation at break measured according to ISO 527
  • the melting point has been measured by using a DSC instrument according to ISO
  • Load cell with natural frequency equal to or greater than 15,000 Hz
  • Some films with a thickness of 50 pm are prepared by extruding each test composition in a single screw Collin extruder (length/diameter ratio of screw 1:25) at a film drawing speed of 7 m/min and a melt temperature do 210-250 °C.
  • Extrusion products and injection-molded articles are produced and assessed following ISO 19069-2: 2016, ISO294-E2017 and ISO294-3:2002.
  • twin screw extruder (Werner-type extruder) were introduced 60% of a virgin propylene homopolymer having a MFR 0.8 g/10’ and 40% of a recycled composition made separately and having a MFR of 4.3 g/10’, made of 80% wt of a recycled random propylene ethylene copolymer containing 4.5% of ethylene, 15% recycled SEBS and 5% of recycled LLDPE.
  • the polymer portion is mixed with a standard additive package (Irgafos).
  • Example 5 It was operated like in example 1 with the difference that were introduced 80% of a virgin propylene random copolymer (component (a)) having a melt flow rate of 1.8 and an ethylene content of 3%wt and 20% (component b) of a recycled composition made separately and having a MFR of 4.3 g/10’, made of 85%wt of a recycled random propylene ethylene copolymer containing 4.5% of ethylene, 8% recycled SEBS and 7% of recycled LLDPE.
  • component (a) a virgin propylene random copolymer having a melt flow rate of 1.8 and an ethylene content of 3%wt and 20%
  • component b of a recycled composition made separately and having a MFR of 4.3 g/10’, made of 85%wt of a recycled random propylene ethylene copolymer containing 4.5% of ethylene, 8% recycled SEBS and 7% of recycled LLDPE.
  • the polymer portion is mixed with a standard additive package (Irgafos).
  • compositions of the present disclosure offer a balance of mechanical and optical properties at the same level of those of the 100% virgin polymers and better than the formulations including recycled material of the prior art.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

The present disclosure relates to polyolefin compositions, in particular polypropylene compositions containing (a) 45 to 90%, of a propylene polymer optionally containing up to 7%wt of ethylene and having a melt flow rate (ISO 1133 230°C/2.16 kg) ranging from 0.5 to 5g/10'; (b) from 10 to 55% of a multicomponent recycled composition containing at least 70 % by weight, of a propylene polymer containing from 1 to 7% by weight of ethylene and from 5 to 30, by weight of a styrenic block copolymer (SBC). The polyolefin compositions according to the present disclosure find application in extrusion, thermoforming and blow molding applications particularly for manufacturing of bottles.

Description

POLYOLEFIN COMPOSITIONS OBTAINED FROM RECYCLED POLYOLEFINS
FIELD OF THE INVENTION
[0001] The present disclosure relates to compositions containing recycled polypropylene that can be advantageously used for the production of blow molding articles.
BACKGROUND OF THE INVENTION
[0002] Polyolefins, in particular polypropylene, are increasingly consumed in large amounts for many applications, including packaging for food and other goods, fibers, automotive components, and a great variety of manufactured articles. However, the said massive use of polyolefins is creating a concern as regards the environmental impact of the waste materials generated after the first use.
[0003] In fact, large amounts of waste plastic materials are presently coming from differential recovery of municipal plastic wastes, mainly constituted of flexible packaging (cast film, blown film and BOPP film), rigid packaging, blow moulded bottles and injection moulded containers. Usually, through a step of separation from other polymers, such as PVC, PET or PS, two main polyolefinic fractions are obtained, namely polyethylenes (in particular HDPE LDPE, LLDPE) and polypropylenes (homopolymers, random copolymers, heterophasic copolymers). [0004] However, the multicomponent nature of the recycled material often results in low mechanical and optical performances of the polyolefin formulations in which part of the virgin polymer is replaced by recycled polymer.
[0005] In an effort to mitigate the mechanical properties deterioration the use of compatibilizer ingredients has been proposed in the art. US5,030,662 for example discloses the use of compatibilizer of the type that reacts with the polymer matrix under heat and shearing conditions either by free radical or ionic mechanism. Examples of compatibilizers according to this document are olefin copolymers with polar monomers such as maleic anhydride or vinyl acetate.
[0006] W02007/071494 discloses the use of a a heterophasic polyolefin composition having flexural modulus equal to or lower than 600 MPa as a compatibilizer agent for a recycled polyolefin composition. In both cases, the effect of the compatibilizer was that of improving the mechanical properties while the optical properties had not been tested. In fact, improving the optical properties of polyolefin composition including substantial amounts of recycled material is a demanding task because the multiplicity of components chemically different to each other makes certain optical properties such as transparency difficult to be achieved at a satisfactory extent. [0007] As a consequence, the use of recycled material in applications requiring a certain level of transparency, i.e., translucent applications, is strongly discouraged.
[0008] It has now unexpectedly been found that certain specific formulations of recycled material although be based on multiplicity of chemically different components when mixed with virgin polymers generate polyolefin compositions combining good mechanical properties with a level of transparency suited for translucent applications.
SUMMARY OF THE INVENTION
[0009] It is therefore an object of the present disclosure a polypropylene composition comprising, or consisting essentially of, (per cent by weight):
(a) 45 to 90%, preferably 50 to 85%, more preferably 55-80% of a propylene polymer optionally containing up to 7%wt of ethylene and having a melt flow rate (ISO 1133 230°C/2.16 kg) ranging from 0.5 to 5g/10’;
(b) from 10 to 55% preferably from 15 to 50 more preferably from 20 to 45% a recycled composition containing:
(bl) at least 70 %, preferably from 75 to 90% by weight of a propylene polymer containing from 1 to 7% by weight of ethylene;
(b2) from 5 to 30, preferably from 7 to 25% by weight of a styrenic block copolymer (SBC) and, optionally,
(b3)- from 1 to 5% preferably from 2 to 4%, by weight of an ethylene homo or copolymer containing up to 30% wt of a C3-C10 alpha olefin.
DETAILED DESCRIPTION OF THE INVENTION [0010] The term “copolymer” as used herein refers to both polymers with two different recurring units and polymers with more than two different recurring units, such as terpolymers, in the chain. By “ambient temperature” is meant therein a temperature of about 25 °C (room temperature).
[0011] The term “consisting essentially of’, as used herein in connection with a polymer or polymer composition means that, in addition to those components which are mandatory, other components may also be present in the polymer or in the polymer composition, provided that the essential characteristics of the polymer or of the composition are not materially affected by their presence. According to the present disclosure, examples of components that, when present in customary amounts in a polymer or in a polymer composition, do not materially affect their characteristics are the catalyst residues, antistatic agents, melt stabilizers, light stabilizers, antioxidants, antiacids.
[0012] By the term “crystalline polypropylene” is meant in the present application a propylene polymer having an amount of isotactic pentads (mmmm), measured by 13C-MNR on the fraction insoluble in xylene at 25° C, higher than 70 molar %; by “elastomeric” polymer is meant a polymer having solubility in xylene at ambient temperature higher than 50 wt%.
[0013] The features of the components forming the polypropylene composition are not inextricably linked to each other. This means that a certain level of preference of one the features should not necessarily involve the same level of preference of the remaining features of the same or different components. On the contrary, it is intended in the present disclosure that any component (a) to (b3) and any preferred range of features of components (a) to (b3) can be combined with any preferred range of one or more of the features of components (a) to (b3) and with any possible additional component, and its features, described in the present disclosure. [0014] The component (a), which is preferably a virgin resin, can be a propylene homopolymer, a random copolymer of propylene containing up to 7%, preferably 0.2 to 6% of ethylene, or a random terpolymer of propylene containing in addition to ethylene up to 4% by weight, also up to 6% by weight, preferably from 1 to 5%, of a C4-C10 a-olefin. Illustrative C4-C10 a-olefin include 1 -butene, 1-pentene, 1 -hexene, 4-methyl-l-pentene and 1-octene, with 1 -butene being particularly preferred.
[0015] Component (a) has a content of polymer fraction which is insoluble in xylene at room of not less than 80%, more preferably not less than 85%, and most preferably not less than 90% by weight. For propylene homopolymers, the content of polymer which is insoluble in xylene at room temperature is not less than 90%, more preferably not less than 95% and most preferably not less than 97% by weight.
[0016] The melt flow rate (ISO 1133 230°C/2.16 kg) of component (a) preferably ranges from 0.5 to 3g/10’ and preferably from 1 to 3 g/10’. [0017] The melting temperature of the component (a) preferably ranges from 135 to 165°C.
When the component (a) is a homopolymer the melting temperature, determined via DSC, preferably ranges from 155 to 165°C while for a copolymer it preferably ranges from 135 to 155°C. [0018] Component (a) can be prepared by polymerizing propylene, optionally in mixture with ethylene and C4-C10 a-olefin in the presence of a catalyst comprising the product of the reaction between:
[0019] i) a solid catalyst component comprising Ti, Mg, Cl, and at least an internal electron donor compound;
[0020] ii) an alkylaluminum compound and,
[0021] iii) an external electron-donor compound having the general formula:
[0022] (R7)a(R8)bSi(OR9)c, where a and b are integers from 0 to 2, c is an integer from 1 to
4 and the sum (a+b+c) is 4; R7, R8, and R9, are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms.
[0023] The internal donor is preferably selected from the esters of mono or dicarboxylic organic acids such as benzoates, malonates, phthalates and certain succinates. Examples of internal donors are described in US 4522930A, EP 045977A2 and international patent applications WO 00/63261 and WO 01/57099. Particularly suited are the phthalic acid esters and succinate acids esters. Alkylphthalates are preferred, such as diisobutyl, dioctyl and diphenyl phthalate and benzyl- butyl phthalate.
[0024] The particles of solid component (i) may have substantially spherical morphology and average diameter ranging between 5 and 150 pm, preferably from 20 to 100 pm and more preferably from 30 to 90 pm. As particles having substantially spherical morphology, those are meant wherein the ratio between the greater axis and the smaller axis is equal to or lower than 1.5 and preferably lower than 1.3.
[0025] The amount of Mg may preferably range from 8 to 30% more preferably from 10 to
25wt. %.
[0026] The amount of Ti may range from 0.5 to 7% and more preferably from 0.7 to 5wt.
%.
[0027] According to one method, the solid catalyst component (i) can be prepared by reacting a titanium compound of formula Ti(OR)q-yXy, where q is the valence of titanium and y is a number between 1 and q, preferably TiCU, with a magnesium chloride deriving from an adduct of formula MgC12*pROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms. The adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride, operating under stirring conditions at the melting temperature of the adduct (100-130°C). Then, the adduct is mixed with an inert hydrocarbon immiscible with the adduct thereby creating an emulsion which is quickly quenched causing the solidification of the adduct in form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648. The so obtained adduct can be directly reacted with Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130°C) so as to obtain an adduct in which the number of moles of alcohol is of lower than 3, preferably between 0.1 and 2.5. The reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCU; the mixture is heated up to 80-130°C and kept at this temperature for 0.5-2 hours. The treatment with TiC14 can be carried out one or more times. The electron donor compound can be added in the desired ratios during the treatment with TiCU.
[0028] The alkyl-Al compound (ii) is preferably chosen among the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri- n-hexylaluminum, tri-n-octylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides, such as AlEt2Cl and AhE CU, possibly in mixture with the above cited trialkylaluminums. The Al/Ti ratio is higher than 1 and may preferably range between 50 and 2000.
[0029] Particularly preferred are the silicon compounds (iii) in which a is 1, b is 1, c is 2, at least one of R7 and R8 is selected from branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms optionally containing heteroatoms and R9 is a Cl -CIO alkyl group, in particular methyl. Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), diisopropyldimethoxysilane, (2-ethylpiperidinyl)t-butyldimethoxysilane, (2- ethylpiperidinyl)thexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2- ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane. Moreover, are also preferred the silicon compounds in which a is 0, c is 3, R8 is a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and R9 is methyl. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and thexyltrimethoxysilane. [0030] The external electron donor compound (iii) is used in such an amount to give a molar ratio between the organoaluminum compound and said external electron donor compound (iii) of from 0.1 to 200, preferably from 1 to 100 and more preferably from 3 to 50.
[0031] The polymerization process can be carried out in gas-phase, operating in one or more fluidized or mechanically agitated bed reactors, slurry polymerization using as diluent an inert hydrocarbon solvent, or bulk polymerization using the liquid monomer (for example propylene) as a reaction medium.
[0032] Component (b) can origin either from post-consumer waste (PostCW) or from pre consumer waste (Pre-CW). Preferably, it origins from Pre-CW. The pre-consumer plastic is regarded as a plastic waste diverted from a manufacturing process which is not reutilized such as rework, regrind or scrap, and is not reincorporated in the same process that generated it.
[0033] Component (bl) is preferably a random copolymer of propylene containing from 1 to 6%, preferably 2 to 5% of ethylene. It may derive from pre-consumer random PP material used for example packaging.
[0034] Component (b2) is preferably selected from the group consisting of SBS and SEBS rubbers which are (partly) hydrogenated styrene-(ethylene-butadiene)-styrene block copolymers. These polymers are triblock copolymers, having styrene at both extremities of the polymer chain with an internal polybutadiene or ethylene/butadiene, polyisoprene or hydrogenated polybutadiene or polyisoprene block.
[0035] SBC copolymers are obtained via anionic polymerization and are commercially available, for example under the tradenames of Kraton and Tuftec, such as for example Kraton SEBS G1657MS. Also component (b2) is preferably derived from pre-consumer source.
[0036] Preferably, component (b3) is present in an amount ranging from 1 to 5% preferably from 2 to 4%, by weight. It is preferably an ethylene polymer containing up to 30%, preferably up to 20%, more preferably up to 15% by weight of a C3-C10 alpha olefin. Preferably the alpha olefin is selected from butene- 1, hexene- 1 and octene-1.
[0037] The ethylene polymer is preferably selected from LDPE, LLDPE, VLDPE and polyolefin elastomers (POE) of pre-consumer source.
[0038] The melt flow rate (ISO 1133 230°C/2.16 kg) of the whole component (b) can generally range from 0.5 to 30 g/10’, preferably from 1 to 25 glO’ and more preferably from 2 to
20 g/10’. [0039] The component (b) according to the present disclosure preferably has a tensile modulus lower than 500 MPa, preferably lower than 400 MPa.
[0040] The composition forming the component (b) of the present disclosure has preferably a Charpy impact strength at 23°C of 50-100 kJ/m2, more preferably between 55-80 kJ/m2. The Charpy impact strength at -30°C preferably ranges from 5 to 20 kJ/m2, more preferably between from 6 to 15 kJ/m2.
[0041] The component (b) of the present disclosure may exhibit an elongation at break equal to or higher than 400%, and more preferably in the range 500- 600%.
[0042] The melting temperature of component (b) ranges from 140 to 160°C preferably from 145 to 155°C.
[0043] The final melt flow rate (ISO 1133 230°C/2.16 kg) of the whole polypropylene composition ranges from 0.1 to 5g/10’ preferably from 0.5 to 3 g/10’.
[0044] The polypropylene composition can further comprise between 0.05-10wt%, preferably 0.1-8 wt%, of additives.
[0045] Additives may comprise, stabilizers, peroxides, calcium oxides (CaO) or colorants, nucleants, clarifiers and stripping agents.
[0046] A stabilizer can be added, such as for example masterbatches like Tosaf ME
833848, which is a blend of about 70 wt% LDPE with a phenolic stabilizer (Irganox B225) and an Irgafos. Typically, such a masterbatch is added in an amount between 0.2 and 1.5 wt%, preferably between 0.3 and 1.2 wt%.
[0047] A peroxide, in the form of an organic compound or masterbatch can be added. The peroxide improves the flow of the material and can be used to achieve a desired melt flow.
[0048] The peroxide can for example be selected from the group of Zebraflow T028,
Zebraflow T0214 or Zebraflow T0318, which are masterbatches of a peroxide with a polyolefin. The specific amount of peroxide is determined by the skilled in the art having in mind the melt flow rate of the single components, their respective amounts and the final desired melt flow rate. As an example, the peroxide can amount to 2-10 wt% of the entire additive package.
[0049] A CaO can be added to inhibit release of HC1. The CaO can be also added as a masterbatch with for example LDPE. CaO can for example be added in a range between 0-2 wt%. [0050] A black colorant can for example be added to the polymer composition between
0.1-5 wt%, preferably between 1-2 wt% in the form of a masterbatch blend. [0051] Stripping agents are compounds used to remove volatiles during processing of the composition. BYK 4200 is one of the commercially available products.
[0052] The amount of the whole package of additives ranges from 0.5 to 7%wt preferably from 1 to 6%wt based on the total amount of the polypropylene composition.
[0053] In a preferred embodiment of the present disclosure, the polypropylene composition consists of the following components (per cent by weight):
(a) 45 to 90%, preferably 50 to 85%, more preferably 55-80% of a propylene polymer optionally containing up to 7%wt of ethylene and having a melt flow rate (ISO 1133 230°C/2.16 kg) ranging from 0.5 to 5g/10’;
(b) from 10 to 55% preferably from 15 to 50 more preferably from 20 to 45% a recycled composition containing:
(bl) at least 70 %, preferably from 75 to 90% by weight of a propylene polymer containing from 1 to 7% by weight of ethylene;
(b2) from 5 to 30, preferably from 7 to 25% by weight of a styrenic block copolymer (SBC) and, (b3) from 1 to 5% preferably from 2 to 4%, by weight of an ethylene homo or copolymer containing up to 30% wt of a C3-C10 alpha olefin; said polypropylene composition further consisting of - 0.05- 10 wt%, preferably 0.1-8 wt%, of additives.
[0054] The propylene polymer composition according to the present disclosure preferably has a tensile modulus ranging between 800-1400 MPa, preferably between 870-1200 MPa.
[0055] The polymer composition preferably has a Charpy impact strength at 23 °C of 50-
100 kJ/m2, more preferably between 60-90 kJ/m2. The Charpy impact strength at 0°C ranges from 5 to 20 kJ/m2, more preferably between from 6 to 15 kJ/m2.
[0056] The composition of the present disclosure may exhibit a stress at yield equal to or higher than 15 MPa, an elongation at break equal to or higher than 500%, and more preferably higher than 550% and even more preferably equal to or higher than 580%.
[0057] In terms of optical properties the composition of the present disclosure shows a haze level below 30%, preferably below 25% and more preferably below 20%.
[0058] The composition of the present disclosure can be obtained by mechanical blending of the components (a)-(b) and optionally further components and additives according to conventional techniques. [0059] The process of making the polymer composition may use a co-rotating twin screw tandem extruder to which the components (a-b) and optionally further components and additives are added.
[0060] Additives can be added in a reclaim extruder (first extruder) and a compounding extruder (second extruder) of a tandem extruder.
[0061] The polypropylene polymer composition can be presented in granule or flake form to be used for manufacturing articles.
[0062] The polypropylene polymer composition of the present disclosure can be used in a variety of applications where an optical/mechanical balance is required. Accordingly, they are suitable for use in the manufacturing of extruded and/or thermoformed articles and particularly suitable for manufacturing blow molded articles and in particular bottles.
[0063] The following examples are given in order to illustrate, but not limit the present disclosure.
EXAMPLES
CHARACTERIZATIONS Xylene-soluble (XS) Fraction at 25 °C
[0064] 2.5 g of polymer and 250 ml of xylene are introduced in a glass flask equipped with a refrigerator and a magnetic stirrer. The temperature is raised in 30 minutes up to the boiling point of the solvent. The resulting clear solution is then kept under reflux and stirred for 30 minutes. The closed flask is then kept for 30 minutes in a bath of ice and water, then in a thermostatic water bath at 25 °C for 30 minutes. The resulting solid is filtered on quick filtering paper. 100 ml of the filtered liquid is poured in a previously weighed aluminum container, which is heated on a heating plate under nitrogen flow to remove the solvent by evaporation. The container is then kept on an oven at 80 °C under vacuum until a constant weight is obtained. The weight percentage of polymer soluble in xylene at room temperature is then calculated.
[0065] The content of the xylene-soluble fraction is expressed as a percentage of the original 2.5 grams and then, by the difference (complementary to 100%), the xylene insoluble percentage (%);
XS of components B) and C) have been calculated by using the formula: XStot=WaXSA+WbXSB+WcXSC wherein Wa, Wb and Wc are the relative amount of components A, B and C, respectively, and (A+B+C=l).
Melt Flow Rate (MFR)
[0066] Measured according to ISO 1133 at 230 °C with a load of 2.16 kg, unless otherwise specified.
Intrinsic Viscosity (IV)
[0067] The sample is dissolved in tetrahydronaphthalene at 135 °C and then poured into a capillary viscometer. The viscometer tube (Ubbelohde type) is surrounded by a cylindrical glass jacket; this setup allows for temperature control with a circulating thermostatic liquid. The downward passage of the meniscus is timed by a photoelectric device.
[0068] The passage of the meniscus in front of the upper lamp starts the counter which has a quartz crystal oscillator. The meniscus stops the counter as it passes the lower lamp and the efflux time is registered: this is converted into a value of intrinsic viscosity through Huggins' equation (Huggins, M.L., J. Am. Chem. Soc., 1942, 64, 2716) provided that the flow time of the pure solvent is known at the same experimental conditions (same viscometer and same temperature). One single polymer solution is used to determine [ q ].
Ethylene (C2) content
13C NMR of propylene/ethylene copolymers
[0069] 13C NMR spectra were acquired on a Bruker AV-600 spectrometer equipped with cryoprobe, operating at 160.91 MHz in the Fourier transform mode at 120°C.
[0070] The peak of the Spp carbon (nomenclature according to “Monomer Sequence
Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Mode ” C. J. Carman, R. A. Harrington and C. E. Wilkes, Macromolecules, 1977, 10, 536) was used as internal reference at 29.9 ppm. The samples were dissolved in 1,1,2,2-tetrachloroethane- d2 at 120°C with a 8 % wt/v concentration. Each spectrum was acquired with a 90° pulse, 15 seconds of delay between pulses and CPD to remove 1H-13C coupling. 512 transients were stored in 32K data points using a spectral window of 9000 Hz.
[0071] The assignments of the spectra, the evaluation of triad distribution and the composition were made according to Kakugo (“Carbon- 13 NMR determination of monomer sequence distribution in ethylene-propylene copolymers prepared with d-titanium trichloride- diethylaluminum chloride” M. Kakugo, Y. Naito, K. Mizunuma and T. Miyatake, Macromolecules, 1982, 15, 1150) using the following equations:
PPP = 100 Tpp/S PPE = 100 Tp5/S EPE = 100 Tdd/S
PEP = 100 Spp/S PEE= 100 Sp5/S EEE = 100 (0.25 Sy5+0.5 S56)/S
S = Tbb + Trd + Tdd + Spp + Sp6 + 0.25 Sy6 + 0.5 S66
[0072] The molar percentage of ethylene content was evaluated using the following equation:
E% mol = 100 * [PEP+PEE+EEE]The weight percentage of ethylene content was evaluated using the following equation:
100 * E% mol * MWE
E% wt. = .
E% mol * MWE + P% mol * MWP
[0073] where P% mol is the molar percentage of propylene content, while MWE and MWp are the molecular weights of ethylene and propylene, respectively.
[0074] The product of reactivity ratio r\n was calculated according to Carman (C.J.
Carman, R.A. Harrington and C.E. Wilkes, Macromolecules, 1977; 10, 536) as:
[0075] The tacticity of Propylene sequences was calculated as mm content from the ratio of the PPP mmTpp (28.90-29.65 ppm) and the whole Tpp (29.80-28.37 ppm).
[0076] Ethylene C2 content of component b2 has been measured by measuring the C2 content on component B) and then calculated by using the formula C2tot=XblC2bl+Xb2C2b2 wherein Xbl and Xb2 are the amounts of components bl and b2 in the composition.
Samples for the mechanical tests
[0077] Samples have been obtained according to ISO 1873-2:2007.
[0078] Charpy impact test is determined according to ISO 179-leA, and ISO 1873-2
[0079] Elongation at yield: measured according to ISO 527. [0080] Elongation at break: measured according To ISO 527
[0081] Stress at break: measured according to ISO 527.
[0082] Tensile Modulus according to ISO 527-2,
Melting point and crystallization point
[0083] The melting point has been measured by using a DSC instrument according to ISO
11357-3, at scanning rate of 20C/min both in cooling and heating, on a sample of weight between 5 and 7 mg., under inert N2 flow. Instrument calibration made with Indium.
DBTT (ductile to brittle transition temperature)
[0084] Measured via a biaxial impact test by means of an impact tester equipped with the following features:
Load cell with natural frequency equal to or greater than 15,000 Hz
Capability to impact with a nominal energy of 16J approx (5.3Kg mass * 30cm falling height)
Hemispheric impactor 1/2" diameter Specimen support 38mm diameter Capability to integrate Force/Time curve [0085] DBTT Test description:
Ten (10) 1.55*38mm injection molded specimens are impacted at several different temperatures in order to find the 3 temperatures at which a ratio of 20-80%, 40-60%, 80-20%, respectively, of Brittle/Ductile failures occurs.
As Brittle failure is intended a failure absorbing a total energy equal to or lower than 2 Joules, the best interpolation curve is then traced between those 3 temperatures. The temperature where the event of 50% Brittle and 50% Ductile failures occurs is intended to represent the DBTT.
Haze Determination
[0086] Some films with a thickness of 50 pm are prepared by extruding each test composition in a single screw Collin extruder (length/diameter ratio of screw 1:25) at a film drawing speed of 7 m/min and a melt temperature do 210-250 °C.
[0087] 50 pm film specimens have been used. The haze value is measured using a Gardner photometric unit connected to a Hazemeter type UX-10 or an equivalent instrument having G.E. 1209 light source with filter "C". Reference samples of known haze are used for calibrating the instrument according to ASTM D1003. EXAMPLES
[0088] Extrusion products and injection-molded articles are produced and assessed following ISO 19069-2: 2016, ISO294-E2017 and ISO294-3:2002.
Example 1
[0089] In a twin screw extruder (Werner-type extruder) were introduced 60% of a virgin propylene homopolymer having a MFR 0.8 g/10’ and 40% of a recycled composition made separately and having a MFR of 4.3 g/10’, made of 80% wt of a recycled random propylene ethylene copolymer containing 4.5% of ethylene, 15% recycled SEBS and 5% of recycled LLDPE.
[0090] The polymer portion is mixed with a standard additive package (Irgafos
168/Irganox 1010), added with Millad 3988 clarifying agent (1800ppm) and then extruded under nitrogen atmosphere, at a rotation speed of 250 rpm and a melt temperature of 200-250° C.
Comparative example 1
[0091] It was operated like in example 1 with the difference that only virgin polypropylene was used.
Comparative example 2
[0092] It was operated like in example 1 with the difference that only the recycled composition (component b) was used.
Comparative example 3
[0093] It was operated like in example 1 with the difference that 100% of a virgin random propylene copolymer having a melt flow rate of 1.8 and an ethylene content of 4%wt was used.
Comparative example 4
[0094] It was operated like in example 1 with the difference that 40% of virgin random propylene copolymer having a melt flow rate of 0.3 and an ethylene content of 4%wt. was mixed with 50% of recycled PP having MFR of 16g/10’ and 10% bw of the compatibilizer composition HC1 disclosed as component (B) in W02007/071494.
Example 5 [0095] It was operated like in example 1 with the difference that were introduced 80% of a virgin propylene random copolymer (component (a)) having a melt flow rate of 1.8 and an ethylene content of 3%wt and 20% (component b) of a recycled composition made separately and having a MFR of 4.3 g/10’, made of 85%wt of a recycled random propylene ethylene copolymer containing 4.5% of ethylene, 8% recycled SEBS and 7% of recycled LLDPE.
[0096] The polymer portion is mixed with a standard additive package (Irgafos
168/Irganox 1010), added with Millad 3988 clarifying agent (1800ppm) and then extruded under nitrogen atmosphere, at a rotation speed of 250 rpm and a melt temperature of 200-250° C. Example 6
[0097] It was operated like in example 1 with the difference that were introduced 70% of component (a) and 30% of component (b).
Comparative example 7
[0098] It was operated like in example 5 with the difference that were introduced 100% of component (a) was introduced.
Table 1 - Properties of the final compositions [0099] The above data shows that the compositions of the present disclosure offer a balance of mechanical and optical properties at the same level of those of the 100% virgin polymers and better than the formulations including recycled material of the prior art.

Claims

CLAIMS What is claimed is:
1. A polypropylene composition comprising, or consisting essentially of, (per cent by weight):
(a) 45 to 90%, preferably 50 to 85%, more preferably 55-80% of a virgin propylene polymer optionally containing up to 7%wt of ethylene and having a melt flow rate (ISO 1133 230°C/2.16 kg) ranging from 0.5 to 5g/10’;
(b) from 10 to 55% preferably from 15 to 50%, more preferably from 20 to 45%, of a recycled composition containing:
(bl) at least 70%, preferably from 75 to 90% by weight of a propylene polymer containing from 1 to 7% by weight of ethylene;
(b2) from 5 to 30, preferably from 7 to 25% by weight of styrenic block copolymer (SBC) and, optionally,
(b3) from 1 to 5% preferably from 2 to 4%, by weight of an ethylene homo or copolymer containing up to 30%wt of a C3-C10 alpha olefin.
2. The polypropylene compositions according to claim 1 wherein: component (a) ranges from 50 to 85%, by weight; component (b) ranges from 15 to 50 % by weight;
3. The polypropylene compositions according to anyone of claims 1-2 in which component (a) is a random copolymer of propylene containing from 0.2 to 6% of ethylene.
4. The polypropylene composition according to anyone of claim 1-3 in which component (a) has a content of polymer fraction which is insoluble in xylene at 25 °C measured according to the method reported in the specification, of not less than 80%, more preferably not less than 85%.
5. The polypropylene composition according to anyone of claims 1-4 in which component
(a) has a melt flow rate (ISO 1133 230°C/2.16 kg) ranging from 0.5 to 3g/10’ and preferably from 1 to 3 g/10’.
6. The polypropylene composition according to anyone of claims 1-5 in which component
(b) origins from Pre-CW.
7. The polypropylene composition according to anyone of claims 1-5 in which component (bl) is preferably a random copolymer of propylene containing from 1 to 6%, preferably 2 to 5% of ethylene.
8. The polypropylene composition according to anyone of claims 1-7 wherein component (b2) is selected from the group consisting of SBS and SEBS rubbers.
9. The polypropylene composition according to anyone of claims 1-8 wherein component component (b3) is an ethylene polymer containing up to 30%, preferably up to 20%, more preferably up to 15% by weight of a C3-C10 alpha olefin.
10. The polypropylene composition according to anyone of claims 1-8 wherein the melt flow rate (ISO 1133 230°C/2.16 kg) of the whole component (b) ranges from 0.5 to 30 g/10’, preferably from 1 to 25 g/10’ and more preferably from 2 to 20 g/10’.
11. The polypropylene composition according to anyone of claims 1-10 wherein the component (b) has a tensile modulus lower than 500 MPa, preferably lower than 400 MPa measured according to ISO 527-2.
12. The polypropylene composition according to anyone of claims 1-11 wherein the melt flow rate (ISO 1133 230°C/2.16 kg) of the whole polypropylene composition ranges from 0.1 to 5g/10’ preferably from 0.5 to 3 g/10’.
13. The polypropylene composition according to anyone of claim 1-12 endowed with a tensile modulus ranging between 800-1400 MPa, a Charpy impact strength at 23°C measured in accordance with ISO 179-leA, and ISO 1873-2, ranging from 50-100 kJ/m2, a stress at yield, measured in accordance with ISO 1527-2, equal to or higher than 15 MPa, an elongation at break, measured in accordance with ISO 1527-2, equal to, or higher than, 550% and a haze, measured according to the method reported in the specification, below 30%.
14. Extruded and/or thermoformed articles obtained from the composition according to anyone of claims 1-13.
15. Blow molded articles obtained from the composition according to anyone of claims 1-13.
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